Characterization of the proteinaceous matter in marine aerosols

Marine aerosols play a dominant role in the transfer of oceanic material to the atmosphere. Most marine aerosol originates when air bubbles burst at the sea surface ejecting material from the sea surface microlayer and bubble surface layers into the air. Concentrations of chemical compounds in these surface layers often differ from their concentrations in bulk water. We examined the enrichment of aerosols with proteinaceous matter and attempted to characterize the physical nature and sources of this matter. We measured concentrations of dissolved free (DFAA), dissolved combined (DCAA), and particulate (PAA) amino acids, transparent stainable particles (TSP), and bacteria and virus-like particles as carriers of protein, in natural and simulated aerosols. We also evaluated D/L ratios certain amino acids in all amino acid fractions.DFAA and DCAA enriched the aerosols we sampled by 1.2–20 times compared to bulk seawater; PAA enrichment was usually higher (up to 50-fold). Aerosols contained particles typical of seawater, e.g., microorganisms, organic debris, inorganic particles with adsorbed organic matter, but also a large number of semitransparent gel-like particles, which all contained amino acids. Some of these particles were probably scavenged from bulk water, but new particles produced as bubbles burst at the surface comprised at least 10% of total proteinaceous matter in the aerosol. D/L ratios of certain amino acid suggested that the particles were most likely made from dissolved polymers secreted by phytoplankton that were concentrated on bubble surfaces and in the microlayer. Examination with Alcian Blue (a dye that targets carbohydrates) and Coomassie Blue (a dye that targets proteins) showed that most TSP in the aerosols contained both proteins and polysaccharides. Microorganisms enriched the aerosols by up to two orders of magnitude, but contributed less than 4% to the total protein pool.     

Strong ligands for thorium complexation in marine bacteria

The interaction between thorium and marine organisms (cultured heterotrophic bacteria) was experimentally examined by using chemical equilibrium techniques. Thorium (Th) quantitatively reacts with a binding site on bacteria (Alteromonas, Vibrio, Pseudomonas and Flavobacterium) in 0.1 M HCl solution. According to mass balance analysis of adsorption experiment data, Th forms a 1:1 complex with a binding site similar in reactivity among bacteria used in this study, whose conditional stability constants are in the range from 10(6.63) to 10(7.07) M-1 under the experimental conditions of a 0.1 M HCl solution. The mole ratio of the strong ligand to organic carbon in bacteria ranged from 2.3 to 4.3 mmol/mol C. The strong ligand/carbon ratios in bacteria were more than one order of magnitude greater than in phytoplankton, zooplankton or other organic ligands in surface waters. The results suggest that the strong organic ligand reacting with Th is one of the functional groups commonly existing in oceanic microorganisms. The conditional stability constants of the Th complexes with the binding site in marine microorganisms are in the same order of magnitude as that with the strong ligand found in particulate and dissolved organic matter. These findings strongly suggest that the strong ligand in particulate and dissolved organic matter, reacting with trace metals under the conditions of seawater, originates from marine organisms.     

Comparison of pelagic and nepheloid layer marine snow: implications for carbon cycling

Marine snow from upper and mid-water (i.e., pelagic) depths on the California margin is texturally and compositionally different from that traveling in the nepheloid layer. Transmission electron microscopy shows that pelagic marine snow consists primarily of bioclasts (e.g., diatom frustules, foram tests), organic matter, and microbes. These components are entrained as discrete particles or small aggregates μm in diameter) in a loose network of exocellular, muco-polysaccharide material. Clays are infrequent but, when present, are constituents of comparatively compact organic-rich microaggregates. Microbes are abundant and appear to decrease in number with increasing water depth. In contrast, marine snow aggregates collected from just above the sea floor in the nepheloid layer are assemblages of clay particles, clay flocs, and relatively dense clay–organic-rich microaggregates in an exocellular organic matrix. Bioclasts and microorganisms occur only rarely. The prevalence of clay–organic-rich aggregates in the nepheloid layer suggests that, prior to final deposition and burial, marine snow from the pelagic zone is subject to disaggregation and recombination with terrigenous detrital material near or at the sea floor. Results have significant implications for the accumulation and burial rates of organic carbon on continental margins and the aging and bioavailability of sedimentary organic matter. Samples examined were collected offshore of northern and central California.     

Pollutant—particle associations and dynamics in coastal marine environments: a review

A wide variety of substances, including known or potential pollutants, become associated with particles in coastal marine environments. This association may result from: (1) ion exchange, precipitation, or hydrophobic interactions with the particle surface, (2) co-precipitation with iron and manganese hydrous oxide coatings, (3) complexation with organic substances bound or aggregated with particles, (4) incorporation into mineral lattices, organisms or fecal material, or (5) flocculation of colloidal organic and inorganic matter during river and sea water mixing. The transport, accumulation and fate of such chemically-reactive pollutants in coastal marine environments are governed to a great extent by particle dynamics. Understanding of the mechanisms and processes affecting pollutant-particle associations and dynamics allows the prediction of the fate of a wide variety of pollutants in estuarine, coastal and marine environments.     

The role of organic coatings in the enrichment of marine particles with selenium. The fixation of selenite on an adsorbed amino acid

The enrichment of marine particles with selenium cannot be explained as that with metals present in cationic form by complexation with anionic functional groups of adsorbed organic matter. Physicochemical data obtained using a model system are reported. The surface of the particles is modelized by a mercury electrode whose surface charge density can be easily changed, covered by a layer of adsorbed polymers. Studies with different kinds of macromolecules and salts show a specific interaction between adsorbed polyalanine and selenite. The results can be explained by the concordance of the distances between two oxygen atoms in this oxyanion and between two amine groups of the adsorbed polypeptide. A similar mechanism could occur in marine aggregates whatever their nature, as long as they contain amine groups at their surface which result in this concordance. Some prospects derived from the results are discussed.     

Preliminary study on the distribution of nutrients, organic matter, trace metals in sea surface microlayer in Xiamen Bay and Jiulong Estuary

-The enrichment of nutrients (NOa-, NOa-, PO43-), suspended particles, organic matter (POC, PON,DOC) , and trace metals (Cu, Ni, Cd) was determined in the sea surface microlayer of Xiamen Bay and Jiulong Estuary. The mean enrichment factors ([Xi]microlayer/[Xi ]15cm in depth) mostly ranged between 1 . 0 and 2. 0. The dissolved forms were the major forms of the components measured, the enrichment of dissolved organic matter and suspended particles could lead to the changes in the total amount and speciation of nutrients and trace metals. No correlation was observed between sample concentrations, speciation, enrichment factors and sample locations. However, some evidence shows that these parameters are correlated with sea state, indicating the complexity and dynamic nature of the sea surface microlayer.     

Direct determination of surface active substances in natural waters

Advantages of direct determination of surface active substances without sample pretreatment, using the electrochemical method (a.c. polarography) based on the measurement of adsorption effects on the mercury electrode, are illustrated for a number of freshwater and marine samples and phytoplankton culture media. The effects of dilution, filtration and centrifugation of samples were investigated. A high loss of organic material through filtration was observed for selected sea surface microlayer samples and phytoplankton culture media. The samples were compared with different model surfactants and were found to possess similar adsorption characteristics to hydrophobic, fatty surfactants. The freshwater samples were found to be more stable during pretreatment than the marine samples. Humic substances are the predominant surface-active compounds in freshwater systems. The use of a calibration curve for humic material is proposed for the rapid and direct determination of surfactant activity values for freshwater samples.     

The chemical characteristics of aerosols in the Kuroshio area——Ⅰ. Sources and fluxes

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浮游生物对某些化学物质在海洋微表层中富集所起的作用

本文综合分析了浮游生物对有机物、痕量金属、氮磷营养盐在海洋微表层中富集所起的作用。浮游植物和部分浮游细菌释放的溶解有机物大部分具有表面活性且能与痕量金属络合,它们能靠Gibbs吸附富集于微表层,并促成与络合的痕量金属的富集。浮游细菌对微表层中富集的含氮和含磷有机物的分解可能是促成氮磷营养盐在微表层中富集的重要原因。     

Mathematical modeling of biogenic substance transformations and recycling in a subtropical coastal marine ecosystem

A mathematical model describing the biotransformations of organic and mineral compounds of biogenic elements (P, N, and Si) and dissolved organic carbon was applied for a theoretical analysis of the recycling of nutrients in the coastal zone of the Canary water upwelling. The aim of this study was to quantitatively estimate the effect of nutrient recycling on the dynamics of the biomasses of microorganisms as a matter basis for the biological productivity of the marine environment. Model calculations were carried out for four near-shore areas off the Moroccan Sahara using the morphometric data (mean depths, water volumes, and areas) and longterm monthly mean values of the parameters of the marine environment (temperature, light intensity, water transparency, and depth of the thermocline). In the calculations, no account was taken for the flow rates across the boundaries between the areas and only indirect account for the vertical exchange was taken. At the absence of nutrient transfer, the model reproduces particular features of the dynamics of nutrient and detritus concentrations and the biomasses of microorganisms resulting from the internal recycling of organic and mineral substances only. In order to characterize the processes of the biotransformation, the internal fluxes and turnover times of organic and mineral components were estimated together with the biomasses and biological productivities of microorganisms.     

Origin of sedimentary organic matter in the north-western Adriatic Sea

In order to evaluate the origin and the transformation of organic matter on the shallow shelf of the NW Adriatic Sea, organic carbon, total nitrogen and stable isotope ratios of organic carbon were analysed in riverine suspended matter and sediments as well as in marine suspended and sedimentary organic matter, in marine phytoplankton and zooplankton.The deposition of organic matter is influenced by fine sediment concentration. Surface sediments were characterised by highly variable biogeochemical conditions on the sea floor, whereas sub-surface sediments showed a more homogeneous hypoxic/anoxic environment.Low C_org/N ratio and high organic carbon and nitrogen concentrations in riverine suspended organic matter indicate an important contribution of freshwater phytoplankton within rivers, particularly during low flow regimes, which adds to the marine phyto- and zooplankton at shelf locations.In order to evaluate the importance of terrestrial, riverine and marine sources of OM in shelf sediments, a three end-member mixing model was applied to shelf surface sediments using ¹³C/¹²C values for organic matter and N/C ratios. The model showed an elevated contribution of terrestrial organic substances at intermediate depths (10–15 m), mostly corresponding to an area of coarser grain-size, whereas the riverine and marine organic fractions were mainly accumulating near the coast and offshore, respectively.     

海水中腐殖质对溶解态铁的络合及其影响因素

腐殖质(humic substances,简称HS)是地表普遍存在的天然有机物,对海洋中重要的微量营养元素-铁(Fe)的分布及生物地球化学循环具有重要的影响作用。本文对腐殖质的来源、分布及对海水中溶解态铁的迁移转化的影响做了总结,特别论述了其在河口及沿岸水域的行为。大量研究表明河口、沿岸及开放海水中溶解态铁分布的变化可以用腐殖质的浓度及其铁结合能力的变化来解释。腐殖质的络合作用不仅能够阻止溶解态铁(DFe)在河口、沿岸等水域被去除,而且能够通过洋流将DFe迁移至外海及大洋区域,此外还能增加铁的溶解度及对海水中浮游植物的生物可利用性,并且促进铁的氧化还原循环。研究还发现两者之间的络合强度受到盐度、pH等理化因素的影响。盐度是影响HS与DFe配合能力的重要影响因素,盐度增加,导致HS中可以与Fe配合的位点数量降低,配合总量呈现指数降低,而pH的增加可以增加HS与DFe的配合量。另外HS还能影响海水中DFe的氧化还原,并以此影响浮游植物对DFe的吸收利用。因此腐殖质对溶解态铁的有机络合作用是影响其海洋生物地球化学循环的一个重要参数,对进一步研究海水中腐殖质的浓度和分布具有重要的意义。     

Measurements of biomass and activity of neustonic microorganisms

Microlayer samples from a coastal marine area near Marseilles (France) collected in 1979 and 1980 have been analysed for POC, PON, chlorophyll a, ATP, cell counts, carbon fixation and in some cases for heterotrophic activity. Comparison of microlayer data with those of underlying water showed in most cases enrichment of organic matter and microorganisms in the surface microlayer. Carbon fixation values were comparable to those observed at 0·50 m except in the slicks, where phytoneustonic activity was higher than that of the underlying phytoplankton. Though total heterotrophic activity was higher in the surface film, the turnover time was not significantly different in both microlayer and underlying water. Our data show that enrichment is highly dependent on sea conditions; whenever slicks are present, the surface film seems to function like an eutrophic system, including active living material, although detritus is regularly present in large amounts.     

Partitioning of trace metals released from polluted marine aerosols in coastal seawater

Mobilization and transfer of atmospherically transported metals to major suspended particulate matter components in seawater have been studied in a multichamber leaching experiment. Data on the meteorological air mass history, enrichment factors and sequential extraction analysis indicate that the highly polluted marine aerosol samples collected on Helgoland are of anthropogenic origin. A significant fraction of the total cadmium (81%), zinc (58%), copper (41%), and lead (40%) was released in seawater within 1 h. When exposed to the aerosol and artificial suspended particulate matter components for another 100 h, a portion of the released metals ranging from 10 to 60% was readsorbed. Zinc and lead were scavenged by iron/manganese oxides or readsorbed by the aerosol particulates. Of the total scavenged copper portion 67% was bound to phytoplankton cell walls which evidences an ecological impact of the polluted marine aerosols even in the coastal environment.     

Surfactant production by marine phytoplankton

Electrochemical methods based on adsorption of organic molecules at the mercury electrode-solution interface were used to investigate surfactant production by marine phytoplankton. Six species of marine phytoplankton, representing the classes of Bacillariophyceae, Haeptophyceae, Chlorophyceae and Cryptophyceae, were studied in batch cultures.Our experimental results showed that surfactants were produced in culture media by healthy exponential growing cells. The measured response was found to depend on the particular species and the age of the culture.Total surfactant content in culture media generally increased with cell density, while surfactants per cell showed an inverse relation to cell density. However, we found that in Cryptomonas culture medium, during the exponential growth, excretion of the insoluble surfactant material per cell was independent of cell concentration.In addition to culture experiments, surfactant activity at several northern Adriatic stations was measured during various stages of phytoplankton bloom. It was concluded that a significant part of surfactant activity in a seawater column is due to phytoplankton production.     

某电厂煤码头煤尘对海洋环境影响的估算

以广东某电厂煤码头为例，探讨临海煤码头落海煤尘对海洋环境的影响。文中阐述了点源和面源起尘量的估算。根据风速、煤粒下降速度、落差高度等计算煤码头扬尘入海量。依据煤尘煤粒到达海区的量计算煤尘入海引起海水悬浮物的增量等。文中还讨论了落海煤尘煤粒对海洋环境水质、沉积物和海洋生物的影响，认为其主要是对海水水质悬浮物、海洋生物光合作用以及沉积物有机质、硫化物含量的影响等。     

New perspective of Miocene marine hydrocarbon source rocks in deep-water area in Qiongdongnan Basin of northern South China Sea

Drilling wells reveal that the organic matter abundance of Miocene marine source rocks in shallow water area of the Qiongdongnan Basin is relatively low with poor hydrocarbon generation poten- tial. However, in some drilling wells of deep water area close to the central depression belt, Miocene marine source rocks with better organic matter abundance and hydrocarbon generation have been found, which have achieved better source rock standard based on the analysis of geochemical charac- teristics. Although there are no exploratory wells in deep water area of the research region, through the comparative analysis of geochemical data of several typical exploratory wells respectively from shallow water area in the basin, central depression belt margin in deep-water area of the basin and Site 1148 of deep sea drilling in the South China Sea Basin, it reveals that the tendency of the quality of source rocks becomes positive gradually from delta to bathyal environment, which then becomes negative as in deep oceanic environment. Owing to the lack of terrestrial organic matter input, the important controlling factors of Miocene marine source rocks in the Qiongdongnan Basin are ocean productivity and preservation conditions of organic matter. The element geochemistry data indicate that the tendency of the paleoproductivity and the preservation conditions of organic matter become positive as water depth increase from shallow area to bathyal area close to central depression belt. So it is speculated that there must exist high quality source rocks in the central depression area where the preservation conditions of organic matter are much better. Besides, in theory, in oxygen-poor zone of oceanic environment at the water depth 400-1 000 m, the preservation conditions of organic matter are well thus forming high-quality marine source rocks. The result- ing speculation, it is reasonable to consider that there are high hydrocarbon generation potential source rocks in bathyal environment of the Qiongdongnan Basin, especially at the water depth 400- 1 000 m.     

Origin and fate of particulate organic matter in the southern Beaufort Sea – Amundsen Gulf region,Canadian Arctic

To establish the relative importance of terrigenous and marine organic matter in the southern Beaufort Sea, we measured the concentrations and the stable isotopic compositions of organic carbon and total nitrogen in sediments and in settling particles intercepted by sediment traps. The organic carbon content of surface sediment in the Chukchi and southern Beaufort Seas ranged from 0.6 to 1.6% dry wt., without a clear geographical pattern. The C_ORG:N_TOT ratio ranged from 7.0 to 10.4 and did not vary significantly downcore at any one station. Values of δ¹³C_ORG and δ¹⁵N_TOT in the sediment samples were strongly correlated, with the highest values, indicative of a more marine contribution, in the Amundsen Gulf. In contrast, the organic matter content, elemental (C_ORG:N_TOT ratio) and isotopic (δ¹³C_ORG and δ¹⁵N_TOT) composition of the settling particles was different from and much more variable than in the bottom sediments. The isotopic signature of organic matter in the Beaufort Sea is well constrained by three distinct end-members: a labile marine component produced in situ by planktonic organisms, a refractory marine component, the end product of respiration and diagenesis, and a refractory terrigenous component. A three-component mixing model explains the scatter observed in the stable isotope signatures of the sediment trap samples and accommodates an apparent two-component mixing model of the organic matter in sediments. The suspended matter in the water column contains organic matter varying from essentially labile and marine to mostly refractory and terrigenous. As it settles through the water column, the labile marine organic matter is degraded, and its original stable isotope signature changes towards the signature of the marine refractory component. This process continues in the bottom sediment with the result that the sedimentary organic matter becomes dominated by the refractory terrigenous and marine components.     

Purine and pyrimidine bases in marine particles in the Seto Inland Sea, Japan

Purine and pyrimidine bases in marine environmental particles collected in Harima-Nada, the Seto Inland Sea, Japan, were investigated by high performance liquid chromatography.Purines and pyrimidines concentrations varied from 0.3 to 9.3 μg l⁻¹ (n=20) for suspended matter, and 0.3 to 0.6 mg g⁻¹ (n=10) for sinking particles. A good correlation was found between chlorophyll a and purine+pyrimidine bases in suspended matter, indicating that these bases contained in suspended matter originated from phytoplankton.A comparison between several compositional data of the suspended matter and the sinking particles, namely CN ratio, composition of purines and pyrimidines, and percentages of the nitrogen bases relative to total particulate organic nitrogen, demonstrates that the sinking particles were different from suspended matter. Also, from the variety of purine and pyrimidine concentrations of marine particle samples, it was estimated that the decomposition rate of these bases seemed more rapid than decomposition rates of amino acids reported in our earlier study.     

Different parameterizations of marine snow in a 1D-model and their influence on representation of marine snow, nitrogen budget and sedimentation

A model is presented that simulates the formation of marine aggregates from particles of different origin inside a model of pelagic biological processes. Experiments are carried out with parameterizations appropriate for different types of aggregates, using different kinds of physical forcing, and compared to observations of dissolved inorganic nitrogen (DIN), particulate organic nitrogen (PON), marine snow concentration, and sedimentation.The occurrence of large, macroscopically visible aggregates (marine snow) can best be simulated with parameterizations that have been derived from in situ observations of marine snow, but not with a parameterization sufficient for dense particles. The parameterization strongly determines the amount and timing of deep export, as well as the post-bloom development of the food web in the upper layers.Detritus in aggregates plays a role mainly during times when zooplankton are abundant, as e.g. in the western Arabian Sea during Southwest Monsoon. Then the large aggregates as fast sinking vehicles may remove detritus quickly from shallow and mid-water depth, preventing the accumulation of nutrients that are produced via detritus decomposition. In this region, detritus contributes strongly to deep sedimentation. The nitrogen budget at this location with regard to the observations cannot be closed: depending on model type, either the model simulates too high sedimentation, or too high DIN. Possible causes for this mismatch include undercollection by sediment traps, inaccurate representation of physical processes in the model and the neglect of biological processes, such as production of dissolved organic matter or denitrification.